WO2013191177A1 - 環状アジン化合物、その製造方法、及びそれを含有する有機電界発光素子 - Google Patents

環状アジン化合物、その製造方法、及びそれを含有する有機電界発光素子 Download PDF

Info

Publication number
WO2013191177A1
WO2013191177A1 PCT/JP2013/066739 JP2013066739W WO2013191177A1 WO 2013191177 A1 WO2013191177 A1 WO 2013191177A1 JP 2013066739 W JP2013066739 W JP 2013066739W WO 2013191177 A1 WO2013191177 A1 WO 2013191177A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
group
fluorine atom
aromatic
independently
Prior art date
Application number
PCT/JP2013/066739
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
内田　直樹
田中　剛
陽子 本間
尚志 飯田
桂甫 野村
恵理子 太田
華奈 藤田
Original Assignee
東ソー株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東ソー株式会社 filed Critical 東ソー株式会社
Priority to KR1020147029251A priority Critical patent/KR102148539B1/ko
Priority to CN201380030110.6A priority patent/CN104507927A/zh
Publication of WO2013191177A1 publication Critical patent/WO2013191177A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • the present invention relates to a cyclic azine compound having a carbazolyl group substituted with a nitrogen-containing heteroaryl group useful as a component of an organic electroluminescent element, a method for producing the same, and an organic electroluminescent element containing the same.
  • An organic electroluminescent element has a basic structure in which a light-emitting layer containing a light-emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside of the light-emitting layer.
  • This element utilizes light emission (fluorescence or phosphorescence) accompanying exciton deactivation caused by recombination of holes and electrons, and is applied to displays and the like.
  • the hole transport layer is divided into a hole transport layer and a hole injection layer, the light emitting layer is divided into an electron blocking layer, a light emitting layer and a hole blocking layer, and the electron transport layer is divided into an electron transport layer and an electron injection layer. May be configured.
  • Organic electroluminescence devices have begun to be used in various display devices, but further improvements in device performance are required, such as longer life, higher luminous efficiency, and lower drive voltage. More specifically, development of a carrier transport material that achieves a long life, high luminous efficiency, and low driving voltage is required.
  • a carrier transport material that achieves a long life, high luminous efficiency, and low driving voltage is required.
  • an electron injection material and an electron transport material there is a demand for a new material that can drive an element at a low voltage due to excellent electron injectability and electron transport characteristics, has high light emission efficiency, and can drive the element for a long time.
  • An object of the present invention is to provide an electron injecting material and an electron transporting material for achieving long life, high luminous efficiency, and low driving voltage.
  • the present inventors have included a nitrogen-containing heteroaryl group on the carbazolyl group in a cyclic azine compound substituted with a carbazolyl group via a conventionally known arylene group. It has been found that the electron injecting property and the electron transporting property of the cyclic azine compound are remarkably improved by providing the substituent. Further, when such a compound (cyclic azine compound represented by the general formula (1) of the present invention) is used as an electron transport layer in an organic electroluminescence device, compared to the case where a known or general-purpose electron transport material is used. Thus, the present inventors have found that the organic electroluminescent device driving voltage is significantly reduced, the luminous efficiency is improved, and the organic electroluminescent device has a long life, and the present invention has been completed.
  • cyclic azine compound (1) a cyclic azine compound represented by the following general formula (1) (hereinafter referred to as “cyclic azine compound (1)”), a production method thereof, and an organic electroluminescent device containing the same. is there.
  • Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms).
  • Ar 1 and Ar 2 are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
  • Ar 3 is an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
  • Ar 4 each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
  • Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom.
  • n represents an integer of 1 to [the maximum number of bonds -1 that can be formed on Cz-1].
  • Ar 5 is each independently an (m + 1) -valent aryl group having 6 to 30 carbon atoms (each independently having a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an optionally substituted fluorine atom having 3 carbon atoms). Or an aromatic group having 3 to 18 carbon atoms, which may be substituted by an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, may be substituted.
  • Ar 6 is each independently a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
  • Each m independently represents an integer of 1 to [the maximum number of bonds that can be formed on Ar 5 ⁇ 1].
  • the organic electroluminescence device can be driven at a lower voltage, has a higher luminous efficiency, and has a longer life than an organic electroluminescence device using a conventionally known electron transport material. Can be provided.
  • FIG. 46 is a schematic cross-sectional view of a single-layer element manufactured in Example-45.
  • FIG. 46 is a schematic cross-sectional view of a single-layer element manufactured in Example-50 or the like.
  • the present invention relates to the above cyclic azine compound (1), a method for producing the same, and an organic electroluminescent device containing the same.
  • the cyclic azine compound (1) of the present invention is a cyclic azine compound represented by the following general formula (B), (C), or (D) in that the performance as a material for an organic electroluminescent element is good. It is preferable.
  • the substituents in the cyclic azine compound (1) of the present invention are defined as follows, respectively.
  • the alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methyl group, a trifluoromethyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, A tert-butyl group may be mentioned.
  • the aromatic hydrocarbon group having 6 to 18 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group, a phenanthryl group, a perylenyl group, or A triphenylenyl group etc. can be mentioned.
  • the aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom is not particularly limited, and examples thereof include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3- Difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4- Trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,5-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3 , 4,5-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, 2,3,5,6- Trifluoropheny
  • the above-described alkyl group having 1 to 4 carbon atoms is the same aromatic hydrocarbon having 6 to 18 carbon atoms as described above.
  • the aromatic hydrocarbon group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group, a phenanthryl group, a perenylenyl group, and a triphenylenyl group. Groups and the like.
  • the aromatic group having 3 to 18 carbon atoms is not particularly limited, and examples thereof include furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, 2-pyridyl group, 3 -Pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 2-pyrazyl group, 4-pyrazyl group, 5-pyrazyl group, 2-quinolyl group, 3-quinolyl group, 4 -Quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7 -Isoquinolyl group, 8-isoquinolyl group, 9-acridyl group, 2-thi
  • the aromatic group having 3 to 18 carbon atoms having a fluorine atom is not particularly limited, and examples thereof include a fluorofuranyl group, a fluorobenzofuranyl group, a fluorodibenzofuranyl group, a fluorothienyl group, and a fluorobenzothienyl.
  • the above-described alkyl group having 1 to 4 carbon atoms is substituted on the above-described aromatic group having 3 to 18 carbon atoms.
  • methylfuranyl group methylbenzofuranyl group, methyldibenzofuranyl group, methylthienyl group, methylbenzothienyl group, methyldibenzothienyl group, 3-methyl-2-pyridyl group Group, 4-methyl-2-pyridyl group, 5-methyl-2-pyridyl group, 6-methyl-2-pyridyl group, 2-methyl-3-pyridyl group, 4-methyl-3-pyridyl group, 5-methyl -3-pyridyl group, 6-methyl-3-pyridyl group, 2-methyl-4-pyridyl group, 3-methyl-4-pyridyl group, 3,4-dimethyl-2-pyridyl group, 3,5-dimethyl- -Pyridyl group, 3,6-dimethyl-2-pyridyl group, 2,4-dimethyl-3-pyridyl group, 2,5-dimethyl-3-pyridyl group, 2,6-dimethyl-3-
  • the arylene group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a phenylene group, a biphenylylene group, a naphthalene diyl group, an anthracenediyl group, a pyrenediyl group, a terphenylylene group, a phenanthracenediyl group, a perylene diyl group, A triphenylenediyl group etc. can be mentioned.
  • the nitrogen-containing heteroaryl group having 3 to 30 carbon atoms is not particularly limited, and examples thereof include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5 -Pyrimidyl group, 2-pyrazyl group, 4-pyrazyl group, 5-pyrazyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8 -Quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 9-acridyl group, 2-benzothiazolyl group, 4 -Benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzo
  • the (m + 1) -valent aryl group having 6 to 30 carbon atoms (where m is an integer from 1 to [the maximum number of bonds that can be formed on Ar 5 ⁇ 1]) is not particularly limited Examples thereof include an arylene group having 6 to 30 carbon atoms, an aryltriyl group having 6 to 30 carbon atoms, and an aryltetrayl group having 6 to 30 carbon atoms.
  • Ar 5- (Ar 6 ) m represents that m Ar 6 substituents are bonded to Ar 5 . That is, although not particularly limited, for example, when Ar 5 is a phenylene group, m represents an integer of 1 to 5. In addition, m is preferably 1 or 2 and more preferably 1 in terms of good performance as a material for an organic electroluminescent element.
  • Examples of the arylene group having 6 to 30 carbon atoms include the same substituents as the specific examples represented by the arylene group having 6 to 30 carbon atoms.
  • the aryltriyl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include benzenetriyl group, biphenyltriyl group, naphthalenetriyl group, anthracentriyl group, pyrenetriyl group, and terphenyl.
  • a triyl group, a phenanthracenyl group, a perylenetriyl group, a triphenylenetriyl group, and the like can be given.
  • the aryltetrayl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a benzenetetrayl group, a biphenyltetrayl group, a naphthalenetetrayl group, an anthracenetetrayl group, and a pyrenetetrayl group.
  • (N + 1) -valent carbazole group in Cz (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom, Or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms as a substituent), but is not particularly limited.
  • (N + 1) -valent carboline group in Cz (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom, Or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be used as a substituent), but is not particularly limited, but includes a carboline diyl group, carboline tri Yl group, carboline tetrayl group and the like.
  • N represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1], and in the cyclic azine compound (1), Cz- (Ar 4 ) n represents n Ar 4 substituents represented by Cz Indicates that it is bound to.
  • n is preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1 in terms of good performance as a material for an organic electroluminescent element.
  • Cz is not particularly limited, and examples thereof include carbazole-1,9-diyl group, carbazole-2,9-diyl group, carbazole-1,3-diyl group, carbazole-2,7-diyl group, N-phenylcarbazole-2,7-diyl group, N-phenylcarbazole-3,6-diyl group, ⁇ -carboline-2,9-diyl group, ⁇ -carboline-3,9-diyl group, ⁇ -carboline- 4,9-diyl group, ⁇ -carboline-5,9-diyl group, ⁇ -carboline-6,9-diyl group, ⁇ -carboline-7,9-diyl group, ⁇ -carboline-8,9-diyl group , ⁇ -carboline-1,9-diyl group, ⁇ -carboline-3,9-diyl group, ⁇ -carboline-4,
  • Cz is a carbazole-2,9-diyl group, carbazole-3,9-diyl group, carbazole-4,9-diyl group, carbazole-3,6-, because it has good performance as a material for an organic electroluminescent device.
  • Ar 1 or Ar 2 is not particularly limited, but each independently includes, for example, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group, Phenanthryl group, perylenyl group, triphenylenyl group, methylphenyl group, methylbiphenylyl group, methylnaphthyl group, methylanthryl group, methylterphenyl group, methylphenanthryl group, methylperenylenyl group, methyltriphenylenyl group, fluorophenyl group , Fluorobiphenylyl group, fluoronaphthyl group, fluoroanthryl group, fluoroterphenyl group, fluorophenanthryl group, fluoroperenylenyl group, fluorotriphenylenyl group and
  • Ar 1 and Ar 2 are each independently a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group, or a phenanthryl group (these are those that have good performance as a material for an organic electroluminescent device.
  • the group is a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
  • a substituted aromatic group having 3 to 18 carbon atoms may be used as a substituent, and each independently represents a phenyl group, a naphthyl group or a biphenylyl group (these groups are a fluorine atom, a carbon atom, An alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an alkyl group having 1 to 4 carbon atoms substituted with 3 to 18 carbon atoms.
  • Replace aromatic group More preferably to also be) have a, each independently, a phenyl group, methylphenyl group, more preferably a naphthyl group, or a biphenylyl group.
  • phenyl group, biphenylyl group, naphthyl group, anthryl group, pyrenyl group, terphenyl group, or phenanthryl group (these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms) Group, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
  • substituents include, but are not particularly limited to, for example, phenyl group, biphenylyl group, naphthyl group, anthryl group, pyrenyl group, terphenyl group, phenanthryl group, perylenyl group, methylphenyl group, methylbiphenylyl group, Methyl naphthyl group, methyl anthryl group, methyl terphenyl group, methyl phenanthryl group, methyl perylenyl group, fluorophenyl group, Orobifeniriru group, fluoro naphthyl group, fluoro anthryl group, fluorophenyl terphenyl group, fluoro phenanthryl group, and a fluoro peri Les sulfonyl group.
  • phenyl group or biphenylyl group (these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom) Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) is not particularly limited, And phenyl group, biphenylyl group, methylphenyl group, methylbiphenylyl group, fluorophenyl group, fluorobiphenylyl group and the like.
  • Ar 3 is not particularly limited.
  • phenylene group, biphenylylene group, naphthalene diyl group, anthracenediyl group, pyrenediyl group, terphenylylene group, fluorophenylene group, fluorophenyl biphenyl examples thereof include a rylene group, a fluoronaphthalene dil group, a phenyl phenylene group, a phenyl biphenylylene group, a phenyl naphthalene dil group, a naphthyl phenylene group, a naphthyl biphenylylene group, and a naphthyl naphthalene dil group.
  • Ar 3 is a phenylene group or a biphenylylene group (these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms) in terms of good performance as a material for an organic electroluminescent device. Or an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, as a substituent.
  • each independently, a phenylene group, a biphenylylene group, or a fluorophenylene group is more preferable.
  • phenylene group or biphenylylene group (however, these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom) Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) is not particularly limited, Phenylene group, biphenylylene group, naphthalene dil group, terphenylylene group, fluorophenylene group, fluoro naphthalene dil group, phenylphenylene group, phenyl naphthalene dil group, naphthyl phenylene group, naphthyl naphthalene dil group and the like.
  • Ar 5 is not particularly limited.
  • benzenetriyl group methylbenzenetriyl group, biphenyltriyl group, naphthalenetriyl group, anthracentriyl group, pyrenetriyl group, terphenyltriyl group, fluorobenzenetriyl Group, fluorophenylbiphenyltriyl group, fluoronaphthalenetriyl group, phenylbiphenyltriyl group, phenylnaphthalenetriyl group, naphthylbenzenetriyl group, naphthylbiphenyltriyl group, naphthylnaphthalenetriyl group, and the like.
  • Ar 5 is a (m + 1) -valent benzene group or a (m + 1) -valent biphenyl group (these groups are each independently a fluorine atom, carbon number 1 in that the performance as an organic electroluminescent device material is good.
  • An alkyl group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms Group may be present as a substituent).
  • an (m + 1) -valent benzene group (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or 1 carbon atom)
  • a benzenetriyl group, a methylbenzenetriyl group, a fluorobenzenetriyl group, and a naphthylbenzenetriyl group are preferable, and a benzenetriyl group is more preferable.
  • an (m + 1) -valent biphenyl group (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or 1 carbon atom)
  • a biphenyltriyl group, a terphenyltriyl group, a fluorophenylbiphenyltriyl group, and a naphthylbiphenyltriyl group are preferable, and a biphenyltriyl group is more preferable.
  • a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms represented by Ar 4 and Ar 6 (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or 3 to 18 carbon atoms) Or a C 3-18 aromatic group substituted with a C 1-4 alkyl group having a fluorine atom, or a C 3-18 aromatic group substituted with a C 1-4 alkyl group as a substituent.
  • substituent represented by is not particularly limited, for example, each independently, pyridyl group, pyrimidyl group, pyrazyl group, quinolyl group, isoquinolyl group, acridyl group, thiazolyl group, benzothiazolyl group, quinazolyl group Quinoxalyl group, naphthyridyl group, thiantenyl group, indolizyl group, azaindolidyl group, fluoropyridyl group, fluoropyrimidyl group, fluoropyrazyl group, full Loquinolyl group, fluoroisoquinolyl group, fluoroacridyl group, fluorothiazolyl group, fluorobenzothiazolyl group, fluoroquinazolyl group, fluoroquinoxalyl group, fluoronaphthylidyl group, fluorothiantenyl group, Fluoroindolidyl group, fluoroazaind
  • Ar 4 and Ar 6 are each independently a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting of carbon, hydrogen, and nitrogen (independently from the viewpoint of good performance as a material for an organic electroluminescent device.
  • An aromatic group having 3 to 18 carbon atoms as a substituent), or a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms composed of only carbon, hydrogen, nitrogen, and sulfur (each independently fluorine 3 carbon atoms substituted by an atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an alkyl group having 1 to 4 carbon atoms To 18 aromatic groups as substituents). It is preferable.
  • An aromatic group having 18 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ) Is more preferable.
  • Ar 4 and Ar 6 are each independently a pyridyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, a pyridylphenyl group, or a compound that is easy to synthesize and has good performance as a material for an organic electroluminescent device.
  • phenyl group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or a carbon number having a fluorine atom)
  • An aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be preferably used as a substituent.
  • a pyridyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, a pyridylphenyl group, or a 1- (3,5-dipyridyl) phenyl group is more preferable, and a pyridyl group is still more preferable.
  • the aforementioned nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (only having a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or a fluorine atom) consisting of only carbon, hydrogen, and nitrogen
  • a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (only a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom)
  • a substituent represented by a group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms) is not particularly limited, For example, pyridyl group,
  • substituents include, but are not limited to, for example, pyridyl group, pyrimidyl group, pyrazyl group, quinolyl group, isoquinolyl group, fluoropyridyl group, fluoropyrimidyl group, fluoropyrazyl group, fluoroquinolyl group , Fluoroisoquinolyl group, methylpyridyl group, methylpyrimidyl group, methylpyrazyl group, methylquinolyl group, methylisoquinolyl group, phenylpyridyl group, phenylpyrimidi Group, phenylpyrazyl group, phenylquinolyl group, phenylisoquinolyl group, pyridylphenyl group, 1- (3,5-dipyridyl) phenyl group, pyrimidylphenyl group, pyrazylphenyl group, quinolylphenyl group, An isoquinolylpheny
  • Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom. Y and Z are preferably nitrogen atoms, or Y is CH and Z is a nitrogen atom in terms of good performance as a material for an organic electroluminescent element.
  • any hydrogen atom in the cyclic azine compound (1) of the present invention may be substituted with a deuterium atom.
  • the cyclic azine compound (1) of the present invention is prepared by the following reaction formula (1), reaction formula (2), reaction formula (3), or reaction formula in the presence of a metal catalyst or a base and a metal catalyst. It can be produced by the method shown in (4).
  • the compound represented by the general formula (2) is referred to as a compound (2).
  • X 1, X 2, X 3 , and examples of the leaving group represented by X 4 is not particularly limited, for example, a chlorine atom, a bromine atom, and an triflate or iodine atom.
  • a bromine atom or a chlorine atom is preferable in that the reaction yield is good.
  • the leaving group represented by M is not particularly limited, but for example, a chlorine atom, a bromine atom, a triflate, an iodine atom, a metal-containing group (for example, Li, Na, MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl 2 , AlBr 2 , Al (Me) 2 , Al (Et) 2 , Al ( i Bu) 2 , Sn (Me) 3 , Sn (Bu) 3 , SnF 3 , ZnR 3 (R 3 is , Etc.), Si (R 4 ) 3 , BF 3 K, B (OR 1 ) 2 , B (OR 2 ) 3 and the like.
  • a metal-containing group for example, Li, Na, MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl 2 , AlBr 2 , Al (Me) 2 , Al (Et
  • Examples of the metal-containing group represented by M include B (OR 1 ) 2 , B (OR 2 ) 3 , ZnR 3 , Si (R 4 ) 3, etc.
  • Examples of ZnR 3 include ZnCl, ZnBr, and ZnI. Can be illustrated.
  • ligands such as ethers and amines may be coordinated with these metal-containing groups, and the type of ligand is not limited as long as it does not inhibit the reaction formula (1). Absent.
  • Si (R 4 ) 3 examples include SiMe 3 , SiPh 3 , SiMePh 2 , SiCl 3 , SiF 3 , Si (OMe) 3 , Si (OEt) 3 , and Si (OMe) 2 OH.
  • B (OR 1 ) 2 examples include B (OH) 2 , B (OMe) 2 , B (O i Pr) 2 , B (OBu) 2 , and B (OPh) 2 .
  • B (OR 1 ) 2 in the case where two R 1 are combined to form a ring containing an oxygen atom and a boron atom can be exemplified by the following (I) to (VII):
  • the compound represented by (II) is preferable in that the yield is good.
  • Examples of B (OR 2 ) 3 include those represented by the following (I) to (III).
  • the cyclic azine compound (1) of the present invention is prepared by reacting the compound (2) and the compound in the presence of a metal catalyst or in the presence of a base and a metal catalyst. (3), or compound (6) and compound (7) can be synthesized by carrying out a coupling reaction as described in each reaction formula.
  • a metal catalyst is a palladium catalyst or a copper catalyst in the reaction of Reaction Formula (1) and Reaction Formula (3) in that the efficiency of the coupling reaction is excellent.
  • reaction of Reaction formula (1) and Reaction formula (3) it is also possible to react by adding a base, and it is preferable to add a base from the point which the reaction yield improves.
  • M is a chlorine atom, bromine atom, triflate, iodine atom, B (OR 1 ) 2 or Si (R 4 ) 3 , it is essential to add a base.
  • the cyclic azine compound (1) of the present invention is compound (4) in the presence of a metal catalyst or in the presence of a base and a metal catalyst.
  • compound (5), or compound (8) and compound (9) can be synthesized by performing a coupling reaction as described in each reaction formula.
  • the metal catalyst is preferably a palladium catalyst or a nickel catalyst in that the efficiency of the coupling reaction is excellent.
  • reaction of Reaction formula (2) and Reaction formula (4) it is also possible to react by adding a base, and it is preferable to add a base from the point which the reaction yield improves.
  • M is a chlorine atom, bromine atom, triflate, iodine atom, B (OR 1 ) 2 or Si (R 4 ) 3 , it is essential to add a base.
  • a phase transfer catalyst may be added in the reactions of the reaction formulas (1) to (4).
  • the phase transfer catalyst is not particularly limited. For example, 18-crown-6-ether or the like can be used. The amount added is an arbitrary amount within a range that does not significantly inhibit the reaction.
  • the metal catalyst used in the reactions of the reaction formulas (1) to (4) is not particularly limited, and examples thereof include a palladium catalyst, a copper catalyst, and a nickel catalyst. Although it does not specifically limit as a palladium catalyst, For example, salts, such as palladium chloride, palladium acetate, trifluoroacetate palladium, palladium nitrate, can be illustrated.
  • ⁇ -allyl palladium chloride dimer palladium acetylacetonato, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert -Butyl) phosphine palladium, dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium and the like.
  • a palladium complex having a tertiary phosphine as a ligand such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert-butyl) phosphinepalladium, is preferable in terms of high yield, and is available. In terms of ease, tri (tert-butyl) phosphine palladium is more preferable.
  • the copper catalyst is not particularly limited, and examples thereof include copper chloride, copper bromide, copper iodide, copper oxide, and copper triflate. Among these, copper oxide and copper iodide are preferable from the viewpoint of excellent coupling reaction efficiency and the like, and copper oxide is more preferable from the viewpoint of easy availability.
  • the nickel catalyst is not particularly limited.
  • nickel chloride nickel bromide, nickel chloride hydrate, dichloro (dimethoxyethane) nickel, dichloro [1,2-bis (diphenylphosphino) ethane] nickel
  • Dichloro [1,3-bis (diphenylphosphino) propane] nickel
  • dichloro 1,4-bis (diphenylphosphino) butane] nickel
  • dichloro 1,1′-bis (diphenylphosphino) ferrocene] nickel
  • the four include nickel complexes having tertiary phosphine as a ligand) and dichloro (N, N, N ′, N′-tetramethylethylenediamine) nickel.
  • dichloro (dimethoxyethane) nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, dichloro (N, N, N ′, N′-tetramethylethylenediamine) nickel are effective in coupling reaction, etc. Is preferable from the viewpoint of superiority, and dichloro [dimethoxyethane) nickel and dichloro [1,4-bis (diphenylphosphino) butane] nickel are more preferable from the viewpoint of availability.
  • tertiary phosphine is added to palladium salt, nickel salt or their complex compounds.
  • the preparation can be performed separately from the reaction and then added to the reaction system, or can be performed in the reaction system.
  • the tertiary phosphine is not particularly limited.
  • triphenylphosphine trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl -4,5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- ( Dicyclohexylphosphino) biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphos Fino)
  • (tert-butyl) phosphine or 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl is preferred because it is readily available and yields are good.
  • the addition amount of the tertiary phosphine is 1 mol of palladium salt, nickel salt or complex thereof (in terms of palladium or nickel atom).
  • the amount is preferably 0.1 to 10 times mol, and more preferably 0.3 to 5 times mol in terms of good yield.
  • a ligand separately to said copper catalyst.
  • the ligand added to the copper catalyst is not particularly limited.
  • 2,2′-bipyridine, 1,10-phenanthroline, N, N, N ′, N′-tetramethylethylenediamine, triphenyl Examples include phosphine, 2- (dicyclohexylphosphino) biphenyl, and the like. Of these, 1,10-phenanthroline is preferred because it is readily available and yields are good.
  • the base that can be used in the reactions of the reaction formulas (1) to (4) is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate. , Potassium acetate, sodium acetate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride and the like. Among these, potassium carbonate, potassium phosphate, or sodium hydroxide is preferable in terms of a good yield.
  • reaction formulas (1) to (4) are preferably carried out in a solvent.
  • the solvent include, but are not limited to, water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol, xylene, and the like. You may use it combining suitably.
  • a mixed solvent of 1,4-dioxane, xylene, toluene and butanol or a mixed solvent of xylene and butanol is preferable in terms of a good yield.
  • the purity of the cyclic azine compound (1) of the present invention can be increased by carrying out treatments such as reprecipitation, concentration, filtration, and purification after completion of the reactions of the reaction formulas (1) to (4).
  • purification by recrystallization, silica gel column chromatography, sublimation, or the like may be performed as necessary.
  • the compound (2) can be produced, for example, using the method disclosed in Hiroshi Yamanaka, “New edition of heterocyclic compounds”, Kodansha, 2004. Arbitrary hydrogen atoms in compound (2) may be substituted with deuterium atoms.
  • the compound (3) is not particularly limited, but for example, the following 3-1 to 3-17 (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a carbon atom having 6 to 18 carbon atoms)
  • substituents are the same as those described above.).
  • Compound (3) is, for example, J.I. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal of Organic, 16th. 10, 941-944, 2008, or Chemistry of Materials, 20, 5951-5953, 2008.
  • any hydrogen atom in compound (3) may be substituted with a deuterium atom.
  • the amount of the palladium catalyst used in the reaction formula (1) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (2) in terms of good yield. It is preferably a double mole (in terms of palladium atom).
  • the amount of the base used in the reaction formula (1) is not particularly limited, but is preferably 1 to 10 times mol per mol of the compound (3), and 1 to 3 in terms of good yield. More preferably, it is a double mole.
  • There is no particular limitation on the molar ratio of the compound (2) and the compound (3) used in the reaction formula (1) but it is preferably 0.2 to 5 times mol per mol of the compound (2). From the viewpoint of good yield, it is more preferably 1 to 3 moles.
  • Compound (4) can be produced, for example, according to the method shown in Synthesis Example-1 in the Examples.
  • any hydrogen atom in the compound (4) may be substituted with a deuterium atom.
  • the compound (5) is not particularly limited, but for example, the following 5-1 to 5-15 (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a group having 3 to 18 carbon atoms)
  • An aromatic group, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
  • the compound of can be illustrated.
  • M has the same definition as M in the general formula (5).
  • Compound (5) is described in, for example, J. Org. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal of Organic, 16th. 10, 941-944, 2008, or Chemistry of Materials, 20, 5951-5953, 2008.
  • any hydrogen atom in the compound (5) may be substituted with a deuterium atom.
  • Reaction formula (2) is a method for producing the cyclic azine compound (1) of the present invention by reacting the compound (4) with the compound (5) in the presence of a palladium catalyst in the presence of a base. Yes, by applying the reaction conditions of the Suzuki-Miyaura reaction, the target product can be obtained in good yield.
  • the amount of the palladium catalyst used in the reaction formula (2) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (5) in terms of good yield. It is preferable that it is a double mole (palladium atom conversion).
  • the amount of the base to be used is not particularly limited, but is preferably 0.5 to 10 times mol for 1 mol of compound (5), and 1 to 3 times mol for a good yield. Is more preferable.
  • the molar ratio of the compound (4) and the compound (5) used in the reaction formula (2) is preferably 0.2 to 5 times moles with respect to 1 mole of the compound (2). More preferably, the molar ratio is 0.3 to 3 times in terms of good yield.
  • Compound (6) can be produced, for example, according to the method shown in Synthesis Example-2 in the Examples.
  • any hydrogen atom in the compound (6) may be substituted with a deuterium atom.
  • the compound (7) is not particularly limited, but for example, the following 7-1 to 7-21 (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a group having 3 to 18 carbon atoms)
  • An aromatic group, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
  • the compound of can be illustrated.
  • X 3 has the same definition as X 3 in the general formula (7).
  • Reaction formula (3) is a method of obtaining the cyclic azine compound (1) of the present invention by reacting the compound (6) with the compound (7) in the presence of a palladium catalyst and a base. be able to.
  • the amount of the palladium catalyst used in the reaction formula (3) is not particularly limited as long as it is a so-called catalyst amount, but is 0.01 to 0.1 to 1 mol of the compound (6) in terms of a good yield.
  • the amount of the base to be used is not particularly limited, but is preferably 0.5 to 10 times mol and more preferably 1 to 3 times mol for 1 mol of the compound (6).
  • reaction formula (3) a phase transfer catalyst represented by 18-crown-6-ether may be added.
  • the reaction of reaction formula (3) is preferably carried out in a solvent in terms of good yield.
  • Compound (8) can be produced, for example, according to the method shown in Synthesis Example 1 in the Examples.
  • any hydrogen atom in compound (8) may be substituted with a deuterium atom.
  • the compound (9) is not particularly limited.
  • the compound (9) includes the following 9-1 to 9-12 (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 6 to 18 carbon atoms).
  • An aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms, and 3 to 18 carbon atoms Or a C 3-18 aromatic group substituted with an alkyl group having 1 to 4 carbon atoms or a C 3-18 aromatic group having a fluorine atom.
  • substituents are the same as those described above.).
  • X 4 has the same definition as X 4 in the general formula (7).
  • Compound (9) is described in, for example, J. Org. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal of Organic, 16th. 10, 941-944, 2008, or Chemistry of Materials, 20, 5951-5953, 2008.
  • any hydrogen atom in the compound (9) may be substituted with a deuterium atom.
  • Reaction formula (4) is a method for producing the cyclic azine compound (1) of the present invention by reacting compound (8) with compound (9) in the presence of a palladium catalyst, optionally in the presence of a base. Yes, by applying the reaction conditions of the Suzuki-Miyaura reaction, the target product can be obtained in high yield.
  • the amount of the palladium catalyst used in the reaction formula (4) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (9) in terms of a good yield. It is preferably a double mole (in terms of palladium atom).
  • the amount of the base used is not particularly limited, but it is preferably 0.5 to 10 times by mole with respect to 1 mole of compound (9), and 1 to 3 times by mole in terms of good yield. Is more preferable.
  • the molar ratio of the compound (8) and the compound (9) used in the reaction formula (4) is preferably 0.2 to 5 times mol per mol of the compound (8). More preferably, it is 0.3 to 3 moles in terms of good yield.
  • the film-forming by a vacuum evaporation method can be mentioned as a preferable example.
  • Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus.
  • the vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is a diffusion pump and a turbo molecular pump that are generally used in that the production tact time in the production of the organic electroluminescent device is short and the production cost is superior. It is preferably about 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 6 Pa that can be reached by a cryopump or the like. Further, the deposition rate is preferably 0.005 to 10 nm / second depending on the thickness of the film to be formed.
  • a thin film for an organic electroluminescence device comprising the 1,3,5-triazine compound (1) can also be produced by a solution coating method.
  • the cyclic azine compound (1) is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate or tetrahydrofuran, and a spin coating method, an inkjet method, a cast using a general-purpose apparatus. Film formation by a method, a dip method or the like is also possible.
  • Example 1 Under an argon stream, 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (500 mg), 3- [4- (2-pyridyl) phenyl] carbazole (606 mg), palladium acetate ( 7.0 mg), 1M-tri (tert-butyl) phosphine in toluene (94 ⁇ L), potassium carbonate (431 mg), and 18-crown-6-ether (82.5 mg) suspended in xylene (7.8 mL). It became cloudy and heated to reflux for 4 hours. The reaction mixture was allowed to cool and water was added.
  • Example-2 Under an argon stream, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (700 mg), 3- [4- (2-pyridyl) phenyl] carbazole (635 mg), palladium acetate ( 8.1 mg), 1M-tri (tert-butyl) phosphine in toluene (108 ⁇ L), potassium carbonate (498 mg), and 18-crown-6 ether (105 mg) were suspended in xylene (9.0 mL). Heated to reflux for 5 hours. The reaction mixture was allowed to cool and water was added.
  • Example-3 Under an argon stream, 2- (5-chlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine (500 mg), 3- [4- (2-pyridyl) phenyl] carbazole (420 mg) , Palladium acetate (5.3 mg), 1M-tri (tert-butyl) phosphine in toluene (71 ⁇ L), potassium carbonate (329 mg), and 18-crown-6 ether (69 mg) were suspended in xylene (6 mL). The mixture was heated to reflux for 21.5 hours. The reaction mixture was allowed to cool and water was added.
  • Example-4 Under an argon stream, 2- (4′-chlorobiphenyl-4-yl) -4,6-diphenyl-1,3,5-triazine (770 mg), 3- [4- (2-pyridyl) phenyl] carbazole (646 mg) ), Palladium acetate (8.2 mg), 1M-tri (tert-butyl) phosphine in toluene (110 ⁇ L), potassium carbonate (507 mg), and 18-crown-6 ether (97 mg) suspended in xylene (9 mL). It became cloudy and heated to reflux for 4 hours. The reaction mixture was allowed to cool and water was added.
  • Example-5 Under a stream of argon, 2-chloro-9- [4- (4,6-diphenyltriazin-2-yl) phenyl] carbazole (715 mg), 4- (2-pyridyl) phenylboronic acid synthesized in Synthesis Example 1 ( 336 mg), palladium acetate (6.3 mg) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (40 mg), 3M-potassium phosphate aqueous solution (1.3 mL) and 1,4- It was suspended in a mixed solution of dioxane (7 mL) and heated to reflux for 16 hours. The reaction mixture was allowed to cool and water was added.
  • Example-6 Under a stream of argon, 4-chloro-9- [4- (4,6-diphenyltriazin-2-yl) phenyl] carbazole (675 mg), 4- (2-pyridyl) phenylboronic acid (317 mg), palladium acetate (6 0.0 mg) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (38 mg) in a mixed solution of 3M aqueous potassium phosphate (1.1 mL) and 1,4-dioxane (13 mL) And heated to reflux for 18 hours. The reaction mixture was allowed to cool and water was added.
  • Example-7 Under an argon stream, 2- (4-bromophenyl) -4,6-di (biphenyl-4-yl) -1,3,5-triazine (500 mg), 3- [4- (2-pyridyl) phenyl] carbazole (326 mg), palladium acetate (4.2 mg), 1M-tri (tert-butyl) phosphine in toluene (56 ⁇ L), potassium carbonate (256 mg), and 18-crown-6 ether (49 mg) were added to xylene (4. 6 mL) and heated to reflux for 3 hours. The reaction mixture was allowed to cool and water was added.
  • Example-8 Under an argon stream, 2- (3,5-dibromophenyl) -4,6-di (4-methylphenyl) -1,3,5-triazine (1000 mg), 4-methyl-1-naphthaleneboronic acid (486 mg) And tetrakis (triphenylphosphine) palladium (47 mg) were suspended in a mixed solvent of 3M aqueous potassium phosphate (1 mL), THF (8 mL) and ethanol (2 mL), and the mixture was stirred at 40 ° C. for 72 hours. The reaction mixture was allowed to cool, and the precipitated solid was filtered.
  • the obtained solid was washed with water, then with methanol, and then with hexane to obtain 978 mg of a pale yellow solid.
  • the obtained yellowish white solid (950 mg), 3- [4- (2-pyridyl) phenyl] carbazole (602 mg), palladium acetate (7.7 mg), toluene solution of 1M-tri (tert-butyl) phosphine (103 ⁇ L) , Potassium carbonate (473 mg) and 18-crown-6-ether (90 mg) were suspended in xylene (8.6 mL) and heated to reflux for 4.5 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was separated by filtration.
  • Example-9 3- [4- (4,6-diphenyltriazin-2-yl) phenyl] carbazole (650 mg), 3,5-di (2-pyridyl) bromobenzene (469 mg) synthesized in Synthesis Example 2 under an argon stream , Palladium acetate (6.2 mg), 1M-tri (tert-butyl) phosphine in toluene (82 ⁇ L), potassium carbonate (379 mg), and 18-crown-6-ether (72 mg) in xylene (6.9 mL) And heated to reflux for 5.5 hours. The reaction mixture was allowed to cool and water was added.
  • Example-10 Under an argon stream, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (660 mg), 3- (2-pyridyl) carbazole (457 mg), palladium acetate (7.6 mg), 1M-tri (tert-butyl) phosphine in toluene (102 ⁇ L), potassium carbonate (470 mg), and 18-crown-6-ether (90 mg) were suspended in xylene (8.5 mL) and heated to reflux for 2 hours. . The reaction mixture was allowed to cool and extracted with chloroform. After the organic layer was distilled off under reduced pressure, methanol was added to precipitate a solid.
  • Example-11 Under an argon stream, 3- [3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (1.19 g), 2-bromopyridine (474 mg), copper oxide (36 mg) 1,10-phenanthroline (45 mg), 18-crown-6-ether (132 mg), and potassium carbonate (864 mg) were suspended in xylene (12.5 mL) and heated to reflux for 15 hours. The reaction mixture was allowed to cool and water was added.
  • Example-12 Under an argon stream, 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) biphenyl] -4,6-diphenyl-1,3,5-triazine ( 1.08 g), 3-bromo-9- (2-pyridyl) carbazole (570 mg), and tetrakis (triphenylphosphine) palladium (102 mg) were suspended in 1,4-dioxane (9.0 mL), and 3M aqueous potassium phosphate solution (1.8 mL) was added, and the mixture was heated to reflux for 27 hours. The reaction mixture was allowed to cool and water was added.
  • Example-13 Under an argon stream, 3- [1-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) -3-yl] -9- (2-pyridyl) carbazole (1.47 g ), 4- (2-pyridyl) phenylboronic acid (597 mg), palladium acetate (11 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (72 mg) were added to xylene (22.
  • Example-14 Under an argon stream, 6- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] -9- (2-pyridyl) - ⁇ -carboline (845 mg), 4- (2-pyridyl) phenylboronic acid (873 mg), palladium acetate (9.7 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (61.7 mg) were added to THF ( 30 mL), 3M aqueous potassium carbonate solution (1.5 mL) was added, and the mixture was heated to reflux for 60 hours. The reaction mixture was allowed to cool and water was added.
  • Example-15 3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (4,6-diphenyl-1,3,5-triazine under argon flow -2-yl) phenyl] -9- (2-pyridyl) carbazole (1.98 g), 2-bromopyridine (0.56 g), tetrakis (triphenylphosphine) palladium (101.5 mg), -Suspended in dioxane (15 mL), further added 3M aqueous potassium carbonate solution (3 mL), and heated to reflux for 17 hours. The reaction mixture was allowed to cool and water was added.
  • Example-16 Under an argon stream, 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] -9-phenyl-6- (2-pyridyl) carbazole (754 mg) , Phenylboronic acid (167 mg), palladium acetate (5.1 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (32.6 mg) were suspended in xylene (9 mL), Further, 3M-potassium carbonate aqueous solution (1.2 mL) was added, and the mixture was heated to reflux for 48 hours. The reaction mixture was allowed to cool and water was added.
  • Example-17 Under an argon stream, 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) -biphenyl-3-yl] carbazole (1.50 g), 2-bromopyridine (515 mg), Copper (I) oxide (20 mg), 1,10-phenanthroline (49 mg), 18-crown-6-ether (143 mg) and potassium carbonate (752 mg) were suspended in xylene (14 mL) and heated to reflux for 15 hours. . The reaction mixture was allowed to cool and water was added.
  • Example-18 Under an argon stream, compound (E-1) (1.13 g), 6-bromo-9- (2-pyridyl) - ⁇ -carboline (749 mg), and bis (triphenylphosphine) palladium dichloride (31 mg) , 4-Dioxane (11 mL), 3M aqueous potassium carbonate solution (1.5 mL) was added, and the mixture was heated to reflux for 18 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane.
  • Example-19 Under an argon stream, compound (E-1) (418 mg), 3-chloro-9- (2-pyridyl) - ⁇ -carboline (240 mg), palladium acetate (3.7 mg), and 2-dicyclohexylphosphino-2 ′ , 4 ′, 6′-triisopropylbiphenyl (22.9 mg) is suspended in 1,4-dioxane (4.1 mL), 3M aqueous potassium carbonate solution (0.54 mL) is added, and the mixture is heated under reflux for 2 hours. did. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane.
  • Example-20 Under an argon stream, compound (E-1) (1.02 g), 3-bromo-6-phenyl-9- (2-pyridyl) carbazole (839 g), and bis (triphenylphosphine) palladium dichloride (28 mg) were The suspension was suspended in 1,4-dioxane (10 mL), 3M-potassium carbonate aqueous solution (1.3 mL) was further added, and the mixture was heated to reflux for 5 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane.
  • Example-21 Under an argon stream, compound (E-1) (1.34 g), 6-bromo-3-phenyl-9- (2-pyridyl) - ⁇ -carboline (1.00 g), and bis (triphenylphosphine) palladium dichloride (35.1 mg) was suspended in 1,4-dioxane (16.7 mL), 3M-potassium carbonate aqueous solution (1.8 mL) was further added, and the mixture was heated to reflux for 19 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration, washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure.
  • Example-22 Under an argon stream, compound (E-1) (701 mg), 6-bromo-9-phenyl-3- (2-pyridyl) - ⁇ -carboline (550 mg), and bis (triphenylphosphine) palladium dichloride (19 mg) were added. The suspension was suspended in 1,4-dioxane (7 mL), 3M aqueous potassium carbonate solution (1 mL) was added, and the mixture was heated to reflux for 40 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration, washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure.
  • Example-23 Under an argon stream, compound (E-1) (1.02 g), 3-bromo-9-phenyl-6- (2-pyridyl) carbazole (839 g), and bis (triphenylphosphine) palladium dichloride (28 mg) The suspension was suspended in 1,4-dioxane (10 mL), 3M-potassium carbonate aqueous solution (1.3 mL) was further added, and the mixture was heated to reflux for 5 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration, washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure.
  • Example-24 Under an argon stream, compound (E-1) (1.53 g), 3-bromo-9-phenyl-6- (pyrazinyl) carbazole (1.20 g), and bis (triphenylphosphine) palladium dichloride (42.1 mg) was suspended in 1,4-dioxane (15 mL), 3M-potassium carbonate aqueous solution (2.0 mL) was further added, and the mixture was heated to reflux for 7 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration, washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure.
  • the obtained solid was purified by silica gel column chromatography (eluent: chloroform), and the target 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3 was obtained.
  • a gray powder yield 1.59 g, yield 75%) of -yl] -9-phenyl-6- (pyrazinyl) carbazole (A-22) was obtained.
  • Example-25 Under an argon stream, the compound (E-2) (628 mg), iodopyrazine (309 mg), copper (I) oxide (7.2 mg), 1,10-phenanthroline (18 mg), 18-crown-6-ether (53 mg) ), Potassium carbonate (276 mg) was suspended in xylene (5.0 mL) and heated to reflux for 18 hours. After allowing the reaction mixture to cool, water and methanol were added.
  • Example-26 Under an argon stream, the compound (E-2) (628 mg), 2-bromopyrimidine (238 mg), copper (I) oxide (7.2 mg), 1,10-phenanthroline (18.0 mg), potassium carbonate (276 mg) , 18-crown-6 (52.9 mg) was suspended in xylene (5.0 mL) and heated at 150 ° C. for 60 hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration.
  • Example-29 N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (586 mg), 9 -Phenanthreneboronic acid (267 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) in toluene (20.0 mL) and 1-butanol Suspended in a mixed solvent (0.6 mL), 3M aqueous potassium carbonate solution (0.6 mL) was added, and the mixture was heated to reflux for 5 hours.
  • Example-30 N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (586 mg), 9 Anthraceneboronic acid (666 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (9.5 mg) in toluene (20.0 mL) and 1-butanol The mixture was suspended in a mixed solvent (0.6 mL), 3M-potassium carbonate aqueous solution (0.6 mL) was added, and the mixture was heated to reflux for 3.5 hours.
  • Example-31 N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (586 mg), 4 -Dibenzothiopheneboronic acid (274 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) in toluene (20.0 mL) and 1- The mixture was suspended in a mixed solvent of butanol (0.6 mL), 3M-potassium carbonate aqueous solution (0.6 mL) was added, and the mixture was heated to reflux for 5 hours.
  • Example-32 N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (586 mg), 3 -Quinolineboronic acid (346 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) in toluene (20.0 mL) and 1-butanol The mixture was suspended in a mixed solvent (0.6 mL), 3M-potassium carbonate aqueous solution (0.6 mL) was added, and the mixture was heated to reflux for 9 hours.
  • Example-33 Under the argon stream, the above 3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (4,6-diphenyl-1,3,5) -Triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole (339 mg), 3-bromo-6-phenylpyridine (129 mg), tetrakis (triphenylphosphine) palladium (11.6 mg) -Suspended in dioxane (2.5 mL), added with 3M aqueous potassium carbonate solution (0.33 mL), and heated to reflux for 20 hours. The reaction mixture was allowed to cool and water was added.
  • Example-34 Under the argon stream, the above 3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (4,6-diphenyl-1,3,5) -Triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole (678 mg), 2-bromodibenzothiophene (316 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ', 4' , 6′-triisopropylbiphenyl (9.5 mg) is suspended in a mixed solvent of toluene (20.0 mL) and 1-butanol (0.6 mL), and 3M aqueous potassium carbonate solution (0.6 mL) is added.
  • Example-35 Under an argon stream, the compound (E-1) (1.02 g), 3-bromo-9- (2-pyridyl) -6- (quinolin-8-yl) carbazole (946 mg) synthesized in Synthesis Example-17, Tetrakis (triphenylphosphine) palladium (46.2 mg) was suspended in 1,4-dioxane (10 mL), 3M aqueous potassium carbonate solution (1.3 mL) was added, and the mixture was heated to reflux for 13 hours. After allowing the reaction mixture to cool, water and methanol were added. The precipitated solid was collected by filtration, washed with water, methanol, and hexane, and the filtered product was dried by heating under reduced pressure.
  • Example-36 Under an argon stream, 2- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -4,6-diphenyl-1,3,5-triazine ( 1.31 g), 3-bromo-9- (2-pyridyl) -6- [4- (2-pyridyl) phenyl] carbazole (1.57 g), tetrakis (triphenylphosphine) palladium (69.3 mg) , 4-Dioxane (20 mL) and a 3M-potassium carbonate aqueous solution (2.0 mL) were suspended in a mixed solvent and heated to reflux for 13 hours.
  • Example-37 Under an argon stream, the compound (E-1) (1.02 g), 3-bromo-6,9-di (2-pyridyl) carbazole (961 mg), palladium acetate (4.5 mg), 2-dicyclohexylphosphino- 2 ′, 4 ′, 6′-triisopropylbiphenyl (19.0 mg) was suspended in 1,4-dioxane (40.0 mL), 3M aqueous potassium carbonate solution (1.3 mL) was added, and the mixture was added at 95 ° C. for 4 hours. Heated for hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration.
  • Example-38 Under an argon stream, 2- (3,5-dibromophenyl) -4,6-diphenylpyrimidine (466 mg), 9-anthraceneboronic acid (233 mg), and tetrakis (triphenylphosphine) palladium (23 mg) were added to 4N-water. The mixture was suspended in a mixed solvent of an aqueous sodium oxide solution (0.5 mL) and THF (2.0 mL), and stirred at 30 ° C. for 3 hours. Thereafter, water was added, and the precipitated solid was filtered, washed with water, then methanol, and then hexane to obtain 500 mg of a yellowish white solid.
  • the organic layer was purified by silica gel chromatography (developing solvent; chloroform), and 3- [4- (2-pyridyl) phenyl] -9- [3- (4,6-diphenylpyrimidin-2-yl) -5- ( An anthracen-9-yl)] phenylcarbazole (B-1) was obtained as a yellow solid (yield 580 mg, yield 72%).
  • Example-40 Under an argon stream, 2- (5-chlorobiphenyl-3-yl) -4,6-diphenylpyrimidine (1.20 g), 3- (2-pyridyl) carbazole (770 mg), palladium acetate (12.8 mg), 1M -Toluene solution of tri (tert-butyl) phosphine (172 ⁇ L), potassium carbonate (791 mg), and 18-crown-6-ether (151 mg) were suspended in xylene (14 mL) and heated to reflux for 44 hours. The reaction mixture was allowed to cool and extracted with chloroform.
  • the organic layer was purified by silica gel chromatography (developing solvent; chloroform), and the target product 3- (2-pyridyl) -9- [5- (4,6-diphenylpyrimidin-2-yl) biphenyl-3-yl was obtained.
  • a brown powder of carbazole (B-3) (yield 949 mg, yield 53%) was obtained.
  • Example-42 Under an argon stream, 9- (2-pyridyl) -9- [3-chloro-5- (4,6-diphenylpyrimidin-2-yl) phenyl] carbazole (585 mg), 4- (2-pyridyl) phenylboronic acid (239 mg), palladium acetate (4.5 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (29 mg), and 3M aqueous potassium carbonate solution (0.8 mL) were added to toluene (4 mL). 0.5 mL) and n-butanol (0.5 mL), and the mixture was heated to reflux for 3 hours.
  • Example-44 Under an argon stream, 4- (4-bromophenyl) -6- (1-naphthyl) -2-phenylpyrimidine (219 mg) synthesized in Synthesis Example-20, 3- (quinoline-8-) synthesized in Synthesis Example-15 Yl) carbazole (162 mg), palladium acetate (2.2 mg), toluene solution (30 ⁇ L) of 1M-tri (tert-butyl) phosphine, potassium carbonate (152 mg), 18-crown-6-ether (26 mg) in xylene ( 2.5 mL) and heated to reflux for 20 hours. The reaction mixture was allowed to cool and then filtered to remove unnecessary substances.
  • Example-45 As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm 2 as shown in FIG. First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa.
  • ITO indium-tin oxide
  • a hole injection layer 2 a hole transport layer 3, a light emitting layer 4, and an electron transport layer 5 are sequentially formed as an organic compound layer on the glass substrate with an ITO transparent electrode shown by 1 in FIG. Layer 6 was deposited.
  • the material which comprises each layer of an organic electroluminescent element was vacuum-deposited by the resistance heating system.
  • As the hole injection layer 2, sublimated and purified CuPc was vacuum-deposited at a film thickness of 25 nm with a film formation rate of 0.06 nm / second.
  • NPD was vacuum-deposited with a film thickness of 45 nm at a film formation rate of 0.30 nm / second.
  • A-1 synthesized in Example 1 of the present invention was vacuum-deposited with a film thickness of 20 nm at a film formation rate of 0.25 nm / second.
  • a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 was formed.
  • the cathode layer 6 is formed by vacuum deposition of lithium fluoride and aluminum in this order at a film thickness of 1.0 nm and 100 nm at a film formation rate of 0.1 nm / second and 0.25 nm / second, respectively. did.
  • Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
  • DEKTAK stylus type film thickness meter
  • this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less.
  • a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin manufactured by Nagase ChemteX Corporation were used.
  • Example-46 An organic electroluminescent device was produced in the same manner as in Example-45, except that A-3 synthesized in Example 3 was used in place of A-1 in the electron transport layer 5 of Example-45.
  • Example-47 An organic electroluminescent device was produced in the same manner as in Example-45, except that A-6 synthesized in Example 6 was used instead of A-1 in the electron transport layer 5 of Example-45.
  • Reference example-1 In the electron transport layer 5 of Example-31, an organic electroluminescent element was produced in the same manner as in Example-45, except that ETL-1 which is a known electron transport material was used instead of A-1.
  • a direct current was applied to the produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON.
  • BM-9 luminance meter of LUMINANCE METER
  • organic electroluminescence was produced in the same manner as in Example 45 except that A-2 was vacuum-deposited at a film formation rate of 0.25 nm / second and a film pressure of 20 nm instead of A-1. An element was produced.
  • Example-49 An organic electroluminescent device was produced in the same manner as in Example-48 except that A-10 synthesized in Example 10 was used in place of A-2 in the electron transport layer 5 of Example-48.
  • Comparative Example-1 An organic electroluminescent device was produced in the same manner as in Example-48 except that ETL-2 described in Patent Document 4 was used in place of A-2 in the electron transport layer 5 of Example-48.
  • a direct current was applied to the produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. The time when the luminance (cd / m 2 ) is reduced by 20%, and the voltage and efficiency when a current is passed through the element at a density of 20 mA / cm 2 are shown below.
  • the cyclic azine compound (1) of the present invention has an electron injection property, electron transport property, driving voltage (voltage [V]), current efficiency (efficiency [efficiency [ cd / A]), and the device lifetime was significantly improved.
  • Example-50 As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used.
  • the substrate was cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning.
  • Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm 2 as shown in FIG.
  • the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa.
  • a hole injection layer 12, a first hole transport layer 13, a second hole transport layer 14, a light emitting layer 15, and an electron transport are formed as an organic compound layer on the glass substrate with an ITO transparent electrode indicated by 11 in FIG.
  • the layer 16 was sequentially formed, and then the cathode layer 17 was formed.
  • the material which comprises each layer of an organic electroluminescent element was vacuum-deposited by the resistance heating system.
  • HTL-1 was vacuum-deposited with a film thickness of 40 nm at a film formation rate of 0.15 nm / second.
  • HAT-CN was vacuum-deposited with a film thickness of 0.025 nm / second and a film thickness of 5 nm.
  • HTL-2 was vacuum-deposited with a film thickness of 25 nm at a film formation rate of 0.15 nm / second.
  • B-2 synthesized in Example 39 of the present invention was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second.
  • the cathode layer 17 is composed of Liq, magnesium / silver (weight ratio 80/20), and silver in this order at a film formation rate of 0.005 nm / second, 0.5 nm / second, and 0.2 nm / second, respectively.
  • Vacuum deposition was performed with film thicknesses of 5 nm, 80 nm, and 20 nm to form a three-layer structure. Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
  • this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less.
  • a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin manufactured by Nagase ChemteX Corporation
  • Example-51 An organic electroluminescent device was produced in the same manner as in Example-50 except that B-3 synthesized in Example 40 was used in place of B-2 in the electron transport layer 16 of Example-50.
  • Example-52 An organic electroluminescent device was produced in the same manner as in Example-50 except that B-4 synthesized in Example 41 was used instead of B-2 in the electron transport layer 16 of Example-50.
  • Example-53 An organic electroluminescent element was produced in the same manner as in Example 50 except that B-5 synthesized in Example 42 was used in place of B-2 in the electron transport layer 16 of Example-50.
  • Example-54 In the electron transport layer 16 of Example-50, an organic electroluminescent device was produced in the same manner as in Example-50 except that B-6 synthesized in Example 43 was used instead of B-2.
  • Comparative Example-2 An organic electroluminescent device was produced in the same manner as in Example-50 except that ETL-3 was used in place of B-2 in the electron transport layer 16 of Example-50.
  • a direct current was applied to the produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON.
  • BM-9 luminance meter
  • TOPCON LUMINANCE METER
  • the luminance decay time during continuous lighting when a current density of 20 mA / cm 2 was passed was measured.
  • the time when the luminance (cd / m 2 ) is reduced by 10%, and the voltage and efficiency when a current is passed through the device at a density of 20 mA / cm 2 are shown below.
  • the cyclic azine compound (1) of the present invention has an electron injection property, electron transport property, driving voltage (voltage [V]), current efficiency (efficiency [efficiency [ cd / A]), and the device lifetime was significantly improved.
  • Example-55 As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm 2 as shown in FIG. First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa.
  • ITO indium-tin oxide
  • a hole injection layer 12, a first hole transport layer 13, a second hole transport layer 14, a light emitting layer 15, and an electron transport are formed as an organic compound layer on the glass substrate with an ITO transparent electrode indicated by 11 in FIG.
  • the layer 16 was sequentially formed, and then the cathode layer 17 was formed.
  • the material which comprises each layer of an organic electroluminescent element was vacuum-deposited by the resistance heating system.
  • HTL-1 was vacuum-deposited with a film thickness of 45 nm at a film formation rate of 0.15 nm / second.
  • HAT-CN was vacuum-deposited with a film thickness of 0.025 nm / second and a film thickness of 5 nm.
  • HTL-2 was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second.
  • A-3 synthesized in Example 3 of the present invention was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second.
  • the cathode layer 17 is composed of lithium fluoride, magnesium / silver (weight ratio 80/20), and silver in this order at a film formation rate of 0.005 nm / second, 0.5 nm / second, and 0.2 nm / second, respectively.
  • Vacuum deposition was performed with a film thickness of 0.5 nm, 80 nm, and 20 nm to form a three-layer structure. Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
  • this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less.
  • a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin manufactured by Nagase ChemteX Corporation were used.
  • Example-56 An organic electroluminescent device was produced in the same manner as in Example 55 except that A-13 synthesized in Example 13 was used in place of A-3 in the electron transport layer 16 of Example-55.
  • Example-57 An organic electroluminescent element was produced in the same manner as in Example 55 except that B-5 synthesized in Example 42 was used in place of A-3 in the electron transport layer 16 of Example-55.
  • Reference example-2 An organic electroluminescent element was produced in the same manner as in Example 55 except that ETL-1 was used in place of A-3 in the electron transport layer 16 of Example-55.
  • a direct current was applied to the produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON.
  • BM-9 luminance meter
  • TOPCON TOPCON
  • the luminance decay time during continuous lighting when a current density of 20 mA / cm 2 was passed was measured.
  • the time when the luminance (cd / m 2 ) is reduced by 20% and the voltage and efficiency when a current is passed through the element at a density of 10 mA / cm 2 are shown below.
  • the cyclic azine compound (1) of the present invention has a driving voltage (voltage [V]), current efficiency (efficiency [cd / A]), and lifetime of the organic electroluminescence device, as compared with conventionally known compounds. It was shown that the properties are excellent.
  • Example-58 As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm 2 as shown in FIG. First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa.
  • ITO indium-tin oxide
  • a hole injection layer 12, a first hole transport layer 13, a second hole transport layer 14, a light emitting layer 15, and an electron transport are formed as an organic compound layer on the glass substrate with an ITO transparent electrode indicated by 11 in FIG.
  • the layer 16 was sequentially formed, and then the cathode layer 17 was formed.
  • the material which comprises each layer of an organic electroluminescent element was vacuum-deposited by the resistance heating system.
  • HTL-1 was vacuum-deposited with a film thickness of 65 nm at a film formation rate of 0.15 nm / second.
  • HAT-CN was vacuum-deposited with a film thickness of 0.025 nm / second and a film thickness of 5 nm.
  • HTL-2 was vacuum-deposited at a film formation rate of 0.15 nm / second to a film thickness of 10 nm.
  • A-12 synthesized in Example 12 of the present invention was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second. Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.3 to 0.5 nm / second.
  • the cathode layer 7 contains Liq, magnesium / silver (weight ratio 80/20), and silver in this order at a film formation rate of 0.005 nm / second, 0.5 nm / second, and 0.2 nm / second, respectively.
  • Vacuum deposition was performed with film thicknesses of 5 nm, 80 nm, and 20 nm to form a three-layer structure. Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
  • this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less.
  • a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin manufactured by Nagase ChemteX Corporation
  • Example-59 An organic electroluminescent device was produced in the same manner as in Example 58 except that A-16 synthesized in Example 16 was used in place of A-12 in the electron transport layer 16 of Example-58.
  • Example-60 An organic electroluminescent device was produced in the same manner as in Example 58 except that A-17 synthesized in Example 18 was used in place of A-12 in the electron transport layer 16 of Example-58.
  • Example-61 An organic electroluminescent element was produced in the same manner as in Example 58 except that A-18 synthesized in Example 19 was used in place of A-12 in the electron transport layer 16 of Example-58.
  • Example-62 An organic electroluminescent device was produced in the same manner as in Example 58 except that A-19 synthesized in Example 20 was used in place of A-12 in the electron transport layer 16 of Example-58.
  • Example-63 An organic electroluminescent device was produced in the same manner as in Example 58 except that A-20 synthesized in Example 21 was used in place of A-12 in the electron transport layer 16 of Example-58.
  • Example-64 In the electron transport layer 16 of Example-58, an organic electroluminescent element was produced in the same manner as in Example 58 except that A-22 synthesized in Example 24 was used instead of A-12.
  • Comparative Example-3 An organic electroluminescent element was produced in the same manner as in Example 58 except that ETL-4 synthesized in Synthesis Example-21 was used in place of A-12 in the electron transport layer 16 of Example-58.
  • a direct current was applied to the produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON.
  • BM-9 luminance meter of LUMINANCE METER
  • the cyclic azine compound (1) of the present invention is superior in the driving voltage (voltage [V]) and life characteristics of the organic electroluminescence device as compared with the conventionally known compounds.
  • the organic electroluminescent device using the cyclic azine compound (1) of the present invention is more remarkable in device characteristics such as driving voltage, current efficiency, and device lifetime of the organic electroluminescent device than the conventionally known compounds. It turns out that it is exceptional.
  • the organic electroluminescent element using the cyclic azine compound of the present invention can be driven for a long time compared to the organic electroluminescent element using the existing material, not only the element using the fluorescent light emitting material,
  • the present invention is extremely useful industrially because it can be applied to various organic electroluminescent devices using phosphorescent materials.
  • the cyclic azine compound of the present invention has high solubility, and it is possible to produce a device using a coating method as well as a vacuum deposition method, and it can be applied as a light emitting host layer in addition to an electron transport layer, In addition to applications such as flat panel displays, it is also useful in lighting applications that require low power consumption.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
PCT/JP2013/066739 2012-06-18 2013-06-18 環状アジン化合物、その製造方法、及びそれを含有する有機電界発光素子 WO2013191177A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020147029251A KR102148539B1 (ko) 2012-06-18 2013-06-18 환상 아진 화합물, 그 제조 방법, 및 그것을 함유하는 유기 전계발광소자
CN201380030110.6A CN104507927A (zh) 2012-06-18 2013-06-18 环状吖嗪化合物、其制造方法、及含有其的有机电致发光元件

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2012-136711 2012-06-18
JP2012136711 2012-06-18
JP2012-247767 2012-11-09
JP2012247767 2012-11-09
JP2012-279641 2012-12-21
JP2012279641 2012-12-21

Publications (1)

Publication Number Publication Date
WO2013191177A1 true WO2013191177A1 (ja) 2013-12-27

Family

ID=49768772

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/066739 WO2013191177A1 (ja) 2012-06-18 2013-06-18 環状アジン化合物、その製造方法、及びそれを含有する有機電界発光素子

Country Status (3)

Country Link
KR (1) KR102148539B1 (ko)
CN (1) CN104507927A (ko)
WO (1) WO2013191177A1 (ko)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014171541A1 (ja) * 2013-04-18 2014-10-23 東ソー株式会社 有機電界発光素子用の複素環化合物及びその用途
WO2014208755A1 (ja) * 2013-06-28 2014-12-31 東ソー株式会社 環状アジン化合物、その製造方法、及びそれを用いた有機電界発光素子
WO2015142036A1 (en) * 2014-03-17 2015-09-24 Rohm And Haas Electronic Materials Korea Ltd. Electron buffering material and organic electroluminescent device comprising the same
WO2015156102A1 (ja) * 2014-04-07 2015-10-15 東ソー株式会社 環状アジン化合物、その製造方法、及びそれを含む有機電界発光素子用材料
KR20160054131A (ko) * 2014-11-05 2016-05-16 삼성디스플레이 주식회사 유기 발광 소자 및 이를 포함하는 표시 장치
WO2016089080A1 (ko) * 2014-12-02 2016-06-09 주식회사 두산 유기 발광 화합물 및 이를 포함하는 유기 전계 발광 소자
US9406892B2 (en) 2015-01-07 2016-08-02 Universal Display Corporation Organic electroluminescent materials and devices
CN106068267A (zh) * 2014-03-17 2016-11-02 罗门哈斯电子材料韩国有限公司 电子缓冲材料和包含其的有机电致发光装置
EP3150604A1 (en) 2015-10-01 2017-04-05 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole carrying benzimidazolo[1,2-a]benzimidazolyl groups, carbazolyl groups, benzofurane groups or benzothiophene groups for organic light emitting diodes
WO2017056053A1 (en) 2015-10-01 2017-04-06 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole carrying benzimidazolo[1,2-a]benzimidazolyl groups, carbazolyl groups, benzofurane groups or benzothiophene groups for organic light emitting diodes
EP3184522A1 (en) * 2015-12-22 2017-06-28 Samsung Electronics Co., Ltd. Condensed cyclic compound, composition including the condensed cyclic compound, organic light-emitting device including the condensed cyclic compound, and method of manufacturing the organic light-emitting device
US20170213983A1 (en) * 2014-11-28 2017-07-27 Idemitsu Kosan Co., Ltd. Compound, organic electroluminescence element material, organic electroluminescence element and electronic device
US9997716B2 (en) 2014-05-27 2018-06-12 Universal Display Corporation Organic electroluminescent materials and devices
WO2019076844A1 (en) * 2017-10-18 2019-04-25 Cynora Gmbh ORGANIC MOLECULES, IN PARTICULAR FOR USE IN OPTOELECTRONIC DEVICES
US10297762B2 (en) 2014-07-09 2019-05-21 Universal Display Corporation Organic electroluminescent materials and devices
US10361375B2 (en) 2014-10-06 2019-07-23 Universal Display Corporation Organic electroluminescent materials and devices
WO2019162332A1 (en) * 2018-02-20 2019-08-29 Cynora Gmbh Organic molecules for optoelectronic devices
US10749113B2 (en) 2014-09-29 2020-08-18 Universal Display Corporation Organic electroluminescent materials and devices
US11189800B2 (en) 2017-07-10 2021-11-30 Lg Chem, Ltd. Heterocyclic compound and organic light emitting device comprising the same
EP4043453A1 (en) 2021-02-11 2022-08-17 Idemitsu Kosan Co., Ltd. Compound, material for an organic electroluminescence device and an organic electroluminescence device comprising the compound
US11522140B2 (en) 2015-08-17 2022-12-06 Universal Display Corporation Organic electroluminescent materials and devices
US11548869B2 (en) * 2017-06-28 2023-01-10 Samsung Display Co., Ltd. Organic molecules for use in organic optoelectronic devices

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101674134B1 (ko) * 2015-04-27 2016-11-08 (주)더블유에스 트리아진 유도체 및 이를 포함한 유기 전계발광 소자
KR102458043B1 (ko) 2015-11-25 2022-10-24 엘지디스플레이 주식회사 유기전계발광소자
CN111808076A (zh) * 2019-04-12 2020-10-23 冠能光电材料(深圳)有限责任公司 一种电子传输空穴阻挡有机材料及其在薄膜发光二极管应用

Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010131930A2 (ko) * 2009-05-15 2010-11-18 제일모직 주식회사 유기광전소자용 화합물 및 이를 포함하는 유기광전소자
WO2011013783A1 (ja) * 2009-07-31 2011-02-03 富士フイルム株式会社 有機電界発光素子
WO2011013681A1 (ja) * 2009-07-31 2011-02-03 富士フイルム株式会社 電荷輸送材料及び有機電界発光素子
WO2011013843A1 (en) * 2009-07-31 2011-02-03 Fujifilm Corporation Organic electroluminescence device
WO2011019156A1 (en) * 2009-08-10 2011-02-17 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011049325A2 (en) * 2009-10-21 2011-04-28 Cheil Industries Inc. Novel compound for organic photoelectric device and organic photoelectric device including the same
WO2011132683A1 (ja) * 2010-04-20 2011-10-27 出光興産株式会社 ビスカルバゾール誘導体、有機エレクトロルミネッセンス素子用材料及びそれを用いた有機エレクトロルミネッセンス素子
WO2011139055A2 (ko) * 2010-05-03 2011-11-10 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2011148909A1 (ja) * 2010-05-24 2011-12-01 出光興産株式会社 有機エレクトロルミネッセンス素子
KR20120009588A (ko) * 2010-07-19 2012-02-02 에스에프씨 주식회사 피리딘 유도체 및 이를 포함하는 유기전계발광소자
WO2012014841A1 (ja) * 2010-07-26 2012-02-02 出光興産株式会社 有機エレクトロルミネッセンス素子
WO2012015274A2 (ko) * 2010-07-30 2012-02-02 롬엔드하스전재재로코리아유한회사 유기발광화합물을 발광재료로서 채용하고 있는 유기 전계 발광 소자
US20120126208A1 (en) * 2010-11-22 2012-05-24 Idemitsu Kosan Co., Ltd. Organic electroluminescence device
WO2012069121A1 (de) * 2010-11-24 2012-05-31 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2012074210A2 (ko) * 2010-12-02 2012-06-07 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2012077902A2 (ko) * 2010-12-08 2012-06-14 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
KR20120072787A (ko) * 2010-12-24 2012-07-04 에스에프씨 주식회사 피리딘 유도체 화합물 및 이를 포함하는 유기전계발광소자
WO2012091279A1 (ko) * 2010-12-31 2012-07-05 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2012108881A1 (en) * 2011-02-11 2012-08-16 Universal Display Corporation Organic light emitting device and materials for use in same
KR20120092908A (ko) * 2011-02-14 2012-08-22 에스에프씨 주식회사 피리딘 유도체 화합물 및 이를 포함하는 유기전계발광소자
KR20120092909A (ko) * 2011-02-14 2012-08-22 에스에프씨 주식회사 피리딘 유도체 화합물 및 이를 포함하는 유기전계발광소자
US20120211736A1 (en) * 2009-11-03 2012-08-23 Cheil Industries, Inc. Compound for organic photoelectric device and organic photoelectric device including the same
WO2012136295A1 (de) * 2011-04-05 2012-10-11 Merck Patent Gmbh Organische elektrolumineszenzvorrichtung
KR20120122813A (ko) * 2011-04-29 2012-11-07 롬엔드하스전자재료코리아유한회사 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자
KR20120122812A (ko) * 2011-04-29 2012-11-07 롬엔드하스전자재료코리아유한회사 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자
JP2012216801A (ja) * 2011-03-28 2012-11-08 Toray Ind Inc 発光素子材料および発光素子
WO2013024872A1 (ja) * 2011-08-18 2013-02-21 出光興産株式会社 ビスカルバゾール誘導体およびこれを用いた有機エレクトロルミネッセンス素子
JP2013035752A (ja) * 2011-08-03 2013-02-21 Idemitsu Kosan Co Ltd ビスカルバゾール誘導体およびこれを用いた有機エレクトロルミネッセンス素子
WO2013089424A1 (ko) * 2011-12-12 2013-06-20 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2013100540A1 (ko) * 2011-12-30 2013-07-04 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2013105206A1 (ja) * 2012-01-10 2013-07-18 出光興産株式会社 有機エレクトロルミネッセンス素子用材料及びそれを用いた素子
WO2013115340A1 (ja) * 2012-02-03 2013-08-08 出光興産株式会社 カルバゾール化合物、有機エレクトロルミネッセンス素子用材料および有機エレクトロルミネッセンス素子

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4404473B2 (ja) 2000-12-25 2010-01-27 富士フイルム株式会社 新規含窒素へテロ環化合物、発光素子材料およびそれらを使用した発光素子
CN1643105A (zh) 2002-03-15 2005-07-20 出光兴产株式会社 有机电致发光装置用材料以及使用这种材料制备的有机电致发光装置
EP2169028B1 (en) 2002-03-22 2018-11-21 Idemitsu Kosan Co., Ltd. Material for organic electroluminescent devices and organic electroluminescent devices made by using the same
JP5399236B2 (ja) 2007-03-26 2014-01-29 新日鉄住金化学株式会社 有機電界発光素子用化合物及び有機電界発光素子
JP5194596B2 (ja) 2007-07-11 2013-05-08 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子、表示装置及び照明装置
SE0900435A1 (sv) * 2009-04-02 2010-06-08 Anna-Kari Sundbaum Oval nål med trubbig spets
TW201301598A (zh) * 2010-11-22 2013-01-01 Idemitsu Kosan Co 有機電激發光元件

Patent Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010131930A2 (ko) * 2009-05-15 2010-11-18 제일모직 주식회사 유기광전소자용 화합물 및 이를 포함하는 유기광전소자
WO2011013783A1 (ja) * 2009-07-31 2011-02-03 富士フイルム株式会社 有機電界発光素子
WO2011013681A1 (ja) * 2009-07-31 2011-02-03 富士フイルム株式会社 電荷輸送材料及び有機電界発光素子
WO2011013843A1 (en) * 2009-07-31 2011-02-03 Fujifilm Corporation Organic electroluminescence device
WO2011019156A1 (en) * 2009-08-10 2011-02-17 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011049325A2 (en) * 2009-10-21 2011-04-28 Cheil Industries Inc. Novel compound for organic photoelectric device and organic photoelectric device including the same
US20120211736A1 (en) * 2009-11-03 2012-08-23 Cheil Industries, Inc. Compound for organic photoelectric device and organic photoelectric device including the same
WO2011132683A1 (ja) * 2010-04-20 2011-10-27 出光興産株式会社 ビスカルバゾール誘導体、有機エレクトロルミネッセンス素子用材料及びそれを用いた有機エレクトロルミネッセンス素子
WO2011132684A1 (ja) * 2010-04-20 2011-10-27 出光興産株式会社 ビスカルバゾール誘導体、有機エレクトロルミネッセンス素子用材料及びそれを用いた有機エレクトロルミネッセンス素子
WO2011139055A2 (ko) * 2010-05-03 2011-11-10 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2011148909A1 (ja) * 2010-05-24 2011-12-01 出光興産株式会社 有機エレクトロルミネッセンス素子
KR20120009588A (ko) * 2010-07-19 2012-02-02 에스에프씨 주식회사 피리딘 유도체 및 이를 포함하는 유기전계발광소자
WO2012014841A1 (ja) * 2010-07-26 2012-02-02 出光興産株式会社 有機エレクトロルミネッセンス素子
WO2012015274A2 (ko) * 2010-07-30 2012-02-02 롬엔드하스전재재로코리아유한회사 유기발광화합물을 발광재료로서 채용하고 있는 유기 전계 발광 소자
US20120126208A1 (en) * 2010-11-22 2012-05-24 Idemitsu Kosan Co., Ltd. Organic electroluminescence device
WO2012069121A1 (de) * 2010-11-24 2012-05-31 Merck Patent Gmbh Materialien für organische elektrolumineszenzvorrichtungen
WO2012074210A2 (ko) * 2010-12-02 2012-06-07 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2012077902A2 (ko) * 2010-12-08 2012-06-14 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
KR20120072787A (ko) * 2010-12-24 2012-07-04 에스에프씨 주식회사 피리딘 유도체 화합물 및 이를 포함하는 유기전계발광소자
WO2012091279A1 (ko) * 2010-12-31 2012-07-05 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2012108881A1 (en) * 2011-02-11 2012-08-16 Universal Display Corporation Organic light emitting device and materials for use in same
KR20120092908A (ko) * 2011-02-14 2012-08-22 에스에프씨 주식회사 피리딘 유도체 화합물 및 이를 포함하는 유기전계발광소자
KR20120092909A (ko) * 2011-02-14 2012-08-22 에스에프씨 주식회사 피리딘 유도체 화합물 및 이를 포함하는 유기전계발광소자
JP2012216801A (ja) * 2011-03-28 2012-11-08 Toray Ind Inc 発光素子材料および発光素子
WO2012136295A1 (de) * 2011-04-05 2012-10-11 Merck Patent Gmbh Organische elektrolumineszenzvorrichtung
KR20120122813A (ko) * 2011-04-29 2012-11-07 롬엔드하스전자재료코리아유한회사 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자
KR20120122812A (ko) * 2011-04-29 2012-11-07 롬엔드하스전자재료코리아유한회사 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자
JP2013035752A (ja) * 2011-08-03 2013-02-21 Idemitsu Kosan Co Ltd ビスカルバゾール誘導体およびこれを用いた有機エレクトロルミネッセンス素子
WO2013024872A1 (ja) * 2011-08-18 2013-02-21 出光興産株式会社 ビスカルバゾール誘導体およびこれを用いた有機エレクトロルミネッセンス素子
WO2013089424A1 (ko) * 2011-12-12 2013-06-20 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2013100540A1 (ko) * 2011-12-30 2013-07-04 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
WO2013105206A1 (ja) * 2012-01-10 2013-07-18 出光興産株式会社 有機エレクトロルミネッセンス素子用材料及びそれを用いた素子
WO2013115340A1 (ja) * 2012-02-03 2013-08-08 出光興産株式会社 カルバゾール化合物、有機エレクトロルミネッセンス素子用材料および有機エレクトロルミネッセンス素子

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9780310B2 (en) 2013-04-18 2017-10-03 Tosoh Corporation Heterocyclic compound for organic electroluminescent device and its application
WO2014171541A1 (ja) * 2013-04-18 2014-10-23 東ソー株式会社 有機電界発光素子用の複素環化合物及びその用途
WO2014208755A1 (ja) * 2013-06-28 2014-12-31 東ソー株式会社 環状アジン化合物、その製造方法、及びそれを用いた有機電界発光素子
CN106068267A (zh) * 2014-03-17 2016-11-02 罗门哈斯电子材料韩国有限公司 电子缓冲材料和包含其的有机电致发光装置
WO2015142036A1 (en) * 2014-03-17 2015-09-24 Rohm And Haas Electronic Materials Korea Ltd. Electron buffering material and organic electroluminescent device comprising the same
CN106068267B (zh) * 2014-03-17 2019-09-03 罗门哈斯电子材料韩国有限公司 电子缓冲材料和包含其的有机电致发光装置
WO2015156102A1 (ja) * 2014-04-07 2015-10-15 東ソー株式会社 環状アジン化合物、その製造方法、及びそれを含む有機電界発光素子用材料
JP2015199681A (ja) * 2014-04-07 2015-11-12 東ソー株式会社 環状アジン化合物、その製造方法、及びそれを含む有機電界発光素子用材料
US9997716B2 (en) 2014-05-27 2018-06-12 Universal Display Corporation Organic electroluminescent materials and devices
US11456423B2 (en) 2014-07-09 2022-09-27 Universal Display Corporation Organic electroluminescent materials and devices
US11957047B2 (en) 2014-07-09 2024-04-09 Universal Display Corporation Organic electroluminescent materials and devices
US10297762B2 (en) 2014-07-09 2019-05-21 Universal Display Corporation Organic electroluminescent materials and devices
US11024811B2 (en) 2014-07-09 2021-06-01 Universal Display Corporation Organic electroluminescent materials and devices
US11641774B2 (en) 2014-09-29 2023-05-02 Universal Display Corporation Organic electroluminescent materials and devices
US10749113B2 (en) 2014-09-29 2020-08-18 Universal Display Corporation Organic electroluminescent materials and devices
US11342510B2 (en) 2014-10-06 2022-05-24 Universal Display Corporation Organic electroluminescent materials and devices
US10361375B2 (en) 2014-10-06 2019-07-23 Universal Display Corporation Organic electroluminescent materials and devices
US20180069181A1 (en) * 2014-11-05 2018-03-08 Samsung Display Co., Ltd. Organic light emitting device and display device including the same
KR102330221B1 (ko) * 2014-11-05 2021-11-25 삼성디스플레이 주식회사 유기 발광 소자 및 이를 포함하는 표시 장치
US10763439B2 (en) 2014-11-05 2020-09-01 Samsung Display Co., Ltd. Organic light emitting device and display device including the same
US11211566B2 (en) 2014-11-05 2021-12-28 Samsung Display Co., Ltd. Organic light emitting device and display device including the same
KR20160054131A (ko) * 2014-11-05 2016-05-16 삼성디스플레이 주식회사 유기 발광 소자 및 이를 포함하는 표시 장치
US10784446B2 (en) * 2014-11-28 2020-09-22 Idemitsu Kosan Co., Ltd. Compound, organic electroluminescence element material, organic electroluminescence element and electronic device
US20170213983A1 (en) * 2014-11-28 2017-07-27 Idemitsu Kosan Co., Ltd. Compound, organic electroluminescence element material, organic electroluminescence element and electronic device
WO2016089080A1 (ko) * 2014-12-02 2016-06-09 주식회사 두산 유기 발광 화합물 및 이를 포함하는 유기 전계 발광 소자
KR20160066339A (ko) * 2014-12-02 2016-06-10 주식회사 두산 유기 발광 화합물 및 이를 포함하는 유기 전계 발광 소자
KR102154878B1 (ko) * 2014-12-02 2020-09-10 두산솔루스 주식회사 유기 발광 화합물 및 이를 포함하는 유기 전계 발광 소자
US9406892B2 (en) 2015-01-07 2016-08-02 Universal Display Corporation Organic electroluminescent materials and devices
US11522140B2 (en) 2015-08-17 2022-12-06 Universal Display Corporation Organic electroluminescent materials and devices
WO2017056053A1 (en) 2015-10-01 2017-04-06 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole carrying benzimidazolo[1,2-a]benzimidazolyl groups, carbazolyl groups, benzofurane groups or benzothiophene groups for organic light emitting diodes
WO2017056052A1 (en) 2015-10-01 2017-04-06 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole carrying benzimidazolo[1,2-a]benzimidazolyl groups, carbazolyl groups, benzofurane groups or benzothiophene groups for organic light emitting diodes
EP3150604A1 (en) 2015-10-01 2017-04-05 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole carrying benzimidazolo[1,2-a]benzimidazolyl groups, carbazolyl groups, benzofurane groups or benzothiophene groups for organic light emitting diodes
EP3184522A1 (en) * 2015-12-22 2017-06-28 Samsung Electronics Co., Ltd. Condensed cyclic compound, composition including the condensed cyclic compound, organic light-emitting device including the condensed cyclic compound, and method of manufacturing the organic light-emitting device
US10597403B2 (en) 2015-12-22 2020-03-24 Samsung Electronics Co., Ltd. Condensed cyclic compound, composition including the condensed cyclic compound, organic light-emitting device including the condensed cyclic compound, and method of manufacturing the organic light-emitting device
US11548869B2 (en) * 2017-06-28 2023-01-10 Samsung Display Co., Ltd. Organic molecules for use in organic optoelectronic devices
US11189800B2 (en) 2017-07-10 2021-11-30 Lg Chem, Ltd. Heterocyclic compound and organic light emitting device comprising the same
WO2019076844A1 (en) * 2017-10-18 2019-04-25 Cynora Gmbh ORGANIC MOLECULES, IN PARTICULAR FOR USE IN OPTOELECTRONIC DEVICES
WO2019162332A1 (en) * 2018-02-20 2019-08-29 Cynora Gmbh Organic molecules for optoelectronic devices
EP4043453A1 (en) 2021-02-11 2022-08-17 Idemitsu Kosan Co., Ltd. Compound, material for an organic electroluminescence device and an organic electroluminescence device comprising the compound

Also Published As

Publication number Publication date
KR20150018776A (ko) 2015-02-24
CN104507927A (zh) 2015-04-08
KR102148539B1 (ko) 2020-08-26

Similar Documents

Publication Publication Date Title
KR102148539B1 (ko) 환상 아진 화합물, 그 제조 방법, 및 그것을 함유하는 유기 전계발광소자
US9624193B2 (en) Cyclic azine derivatives, processes for producing these, and organic electroluminescent element containing these as component
JP6822508B2 (ja) ベンゾチエノピリミジン化合物、その製造方法、及びそれを含有する有機電界発光素子
JP6326930B2 (ja) 有機電界発光素子用複素環化合物及びその用途
JP5761907B2 (ja) １，３，５−トリアジン誘導体とその製造方法、及びそれらを構成成分とする有機電界発光素子
EP2746271B1 (en) Phenyl-substituted 1, 3, 5-triazine compounds as intermediates for electroluminescent molecules
JP6034146B2 (ja) 含窒素縮環芳香族基を有する環状アジン化合物とその製造方法、及びそれらを構成成分とする有機電界発光素子
JP6443107B2 (ja) トリアジン化合物及びその製造方法
WO2012091026A1 (ja) １，３，５－トリアジン化合物とその製造方法、及びそれらを構成成分とする有機電界発光素子
JP6264877B2 (ja) １，２，４−トリス置換ベンゼン化合物、その製造方法、および有機電界発光素子
JP6136616B2 (ja) 環状アジン化合物、その製造方法、及びそれを含有する有機電界発光素子
WO2021079915A1 (ja) ピリジル基を有するトリアジン化合物およびピリジン化合物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13807430

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20147029251

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13807430

Country of ref document: EP

Kind code of ref document: A1